CN107271527B - A kind of method of Electrochemical Detection glyphosate - Google Patents
A kind of method of Electrochemical Detection glyphosate Download PDFInfo
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Abstract
The present invention relates to a kind of method of Electrochemical Detection glyphosate, the synthesis of the material including modified electrode senses the foundation of system.Glyphosate and nitrite anions can form nitrosamine under acid condition, changed by the electrochemical signals that the modified electrode detects nitrite anions, can delicately measure glyphosate.The invention avoids complicated sample pretreatment steps, do not need using large-scale instrument, simple and direct quick, and high sensitivity is suitable for the remaining real-time detection of multiple product glyphosate.
Description
Technical field
The present invention relates to a kind of method of Electrochemical Detection glyphosate, the synthesis of the material including modified electrode senses body
The foundation of system and etc..Glyphosate and nitrite anions easily form nitrosamine in acid condition, influence the oxidation of nitrite anions also
Parent peak realizes the remaining real-time detection of glyphosate.
Background technique
Glyphosate is a kind of wide spectrum, pesticide after non-selective seedling.After the introducing of commercialization in 1974, glyphosate is had become
Leading herbicide is accounted in world wide.Glyphosate is widely used, so that the glyphosate residual in environment is generally existing, this is right
Organism, which is constituted, greatly to threaten.Therefore, glyphosate residual is detected in some samples to be of great significance.
The method of many quantitative detection glyphosates has grown up.For example, the efficient of pre-column derivatization processing need to be carried out
Liquid chromatography, liquid chromatography mass combination, the chromatography of ions, gas chromatography etc..Step is comparatively laborious, needs professional
Operation, equipment instrument are larger and expensive.Therefore, it is badly in need of one kind quickly, accurately, sensitive and lower-cost detection glyphosate
Method.
In acid condition, nitrite anions can form nitrosamine with glyphosate, when glyphosate is added in nitrite anions solution
Afterwards, due to the effect of glyphosate, the redox peaks of nitrite anions change.The present invention is directed to propose one using this principle
The method of the novel Electrochemical Detection glyphosate of kind is to overcome the shortcomings of conventional method.
Summary of the invention
The present invention utilizes fullerene, multi-walled carbon nanotube, gold nanoparticle and PAMAM synthetic composite material PAMAM-C60-
MWCNT-AUNPs, and it is used for modified electrode, modified electrode is used for selective enumeration method glyphosate.
The technical solution of the present invention is as follows:
(1) fullerene, multi-walled carbon nanotube, gold nanoparticle, PAMAM synthetic composite material PAMAM-C60- are utilized
MWCNT-AuNPs, and it is used for modified electrode, the specific steps are that:
It takes 120mg to be graphitized hydroxylated multi-walled carbon nanotubes, the 45mL concentrated sulfuric acid and 15mL concentrated nitric acid is added, it is 2 hours ultrasonic,
Centrifugation is washed with water until PH=6, multi-walled carbon nanotube after must handling in magnetic agitation 12 hours at 90 DEG C later；Injection
1.2mL ice-cold NaBH4(0.1M), which is arrived, contains 0.25mM sodium citrate and 0.25mM HAuCl4Aqueous solution in, stir 6 hours；
Multi-walled carbon nanotube (MWNT) after processing and gold nanoparticle (AuNPs) are mixed 6 hours by 1:10；Take 1.0mg
PAMAM is added under magnetic stirring in 1.0mL ultrapure water, be then added 4.0mL ethyl alcohol continue to stir to get it is evenly dispersed molten
Then above-mentioned mixed solution is added to the C of 1.0mL 1.0mg/mL by liquid60In toluene solution, it is small to be continuously stirred at room temperature 36
When, ethyl alcohol is used respectively, and secondary water washed once to obtain PAMAM-C60；PAMAM-C60It is small that 6 are mixed with MWCNT-AuNPs
When obtain PAMAM-C60-MWCNT-AuNPs；
(2) foundation of Electrochemical Detection glyphosate sensing system, specific steps are as follows:
1. the PAMAM-C for taking 15 μ L to make60For-MWCNT-AuNPs drop coating on glass-carbon electrode, naturally dry obtains modification electricity
Pole PAMAM-C60-MWCNT-AuNPs/GCE；In the PBS buffer solution of pH containing 10mL=6.0 and 10-4mol/L NO2 -Electrolysis
Chi Zhong, with PAMAM-C60- MWCNT-AuNPs/GCE is working electrode, and Ag/AgCl electrode is reference electrode, and platinum electrode is to electricity
Pole；It is tested using CHI760B electrochemical workstation, the acquisition and processing of experimental data are soft using its subsidiary computer
Part, the potential region for carrying out differential pulse voltammetry scanning are set as 0.6 V-1.0V, record complete differential pulse voltammetry figure, survey
Obtain oxidation peak current value Ip0, certain density glyphosate is added in above-mentioned electrolytic cell, and in kind carry out differential pulse
Measurement, measures oxidation peak current value Ip1And calculate peak current difference △ Ip1；
2. the glyphosate standard solution of various concentration according to said method, is added, corresponding peak point current I can be obtainedpnThe peak and
Current differential △ IPn, peak current difference △ IpnGood linear relationship is presented with glyphosate concentration, can detect the linear of glyphosate
Range is 10-12~10-5Mol/L, linear equation are △ Ip(μ A)=8.0241+ 0,4301lgc(mol/L), c is concentration, single
Position is mol/L, peak current IpUnit is μ A, and linearly dependent coefficient r=0.9951 detects and is limited to 6.0 × 10-13mol/L；
3. calculating the concentration of unknown glyphosate using above-mentioned linear equation: in the PBS buffer solution containing 10mlpH=6.0
With 10-4mol/L NO2 -Electrolytic cell in, with PAMAM-C60- MWCNT-AuNPs/GCE is working electrode, and Ag/AgCl electrode is
Reference electrode, platinum electrode are to electrode；Experiment carries out on CHI760B electrochemical workstation, soft using its attached computer
The acquisition and processing of part progress experimental data；Differential pulse scanning is carried out first in 0.6-1.0V potential range, record shows difference
Pulse Voltammetry figure obtains peak point current Ip0, a certain amount of glyphosate solution to be measured is added, similarity condition is scanned, and obtains peak current
Value Ipn, peak current difference △ I is calculatedp, by △ IpIt brings above-mentioned equation into, the dense of solution glyphosate to be measured can be calculated
Degree.
The invention has the benefit that
(1) present invention is prepared for composite material using fullerene, multi-walled carbon nanotube, gold nanoparticle and PAMAM for the first time
PAMAM-C60-MWCNT-AuNPs, and it is used for modified electrode, which can effectively be catalyzed the redox of nitrite anions
Reaction, significantly improves the sensitivity of test experience；
(2) synthetic modification electrode (PAMAM-C60-MWCNT-AuNPs/GCE) of the present invention, preparation step is simple, has good
Good reproducibility and stability, may be reused, cost is relatively low.
(3) PAMAM-C60-MWCNT-AuNPs/GCE prepared by the present invention has preparation step for analyzing measurement glyphosate
Suddenly simply, the characteristics of detection range of linearity is wide, high sensitivity.
Detailed description of the invention:
Fig. 1 show differential pulse voltammetry voltammogram of the glyphosate of various concentration on modified electrode.
The concentration (1) 0, (2) 10 of the standard sample containing glyphosate is respectively indicated in Fig. 1 from 1 to 9-12, (3) 10-11, (4)
10-10, (5) 1.0 × 10-9, (6) 10-8, (7) 10-7, (8) 10-6, (9) 10-5 mol/L。
Specific embodiment:
For a better understanding of the invention, below with reference to specific example to further illustrate the technical scheme of the present invention, still
It cannot be limited the scope of protection of the present invention with following specific examples.
Embodiment 1
(1) fullerene, multi-walled carbon nanotube, gold nanoparticle and PAMAM synthetic composite material PAMAM-C60- are utilized
MWCNT-AuNPs, and it is used for modified electrode, the specific steps are that:
It takes 120mg to be graphitized hydroxylated multi-walled carbon nanotubes, the 45mL concentrated sulfuric acid and 15mL concentrated nitric acid is added, it is 2 hours ultrasonic,
Centrifugation is washed with water until pH=6, multi-walled carbon nanotube after must handling in magnetic agitation 12 hours at 90 DEG C later；Injection
1.2mL ice-cold NaBH4(0.1M), which is arrived, contains 0.25mM sodium citrate and 0.25mM HAuCl4Aqueous solution in, stir 6 hours；
Multi-walled carbon nanotube (MWNT) and gold nanoparticle (AuNP after processingS) be mixed 6 hours by 1:10；Take 1.0mgPAMAM
It is added in 1.0mL ultrapure water under magnetic stirring, 4.0mL ethyl alcohol is then added and continues to stir to get evenly dispersed solution, so
Above-mentioned mixed solution is added to the C of 1.0mL 1.0mg/mL afterwards60In toluene solution, it is continuously stirred at room temperature 36 hours, point
Not Yong ethyl alcohol, secondary water washed once to obtain PAMAM-C60；PAMAM-C60And MWCNT-AuNPSIt is mixed 6 hours and obtains
PAMAM-C60-MWCNT-AuNPs；
(2) foundation of Electrochemical Detection glyphosate sensing system, specific steps are as follows:
1. the PAMAM-C for taking 15 μ L to make60For-MWCNT-AuNPs drop coating on glass-carbon electrode, naturally dry obtains modification electricity
Pole PAMAM-C60-MWCNT-AuNPs/GCE；In the PBS buffer solution of pH containing 10mL=6.0 and 10-4mol/L NO2 -Electrolysis
Chi Zhong, with PAMAM-C60- MWCNT-AuNPs/GCE is working electrode, and Ag/AgCl electrode is reference electrode, and platinum electrode is to electricity
Pole；It is tested using CHI760B electrochemical workstation, the acquisition and processing of experimental data are soft using its subsidiary computer
Part, the potential region for carrying out differential pulse voltammetry scanning are set as 0.6 V-1.0V, record complete differential pulse voltammetry figure, survey
Obtain oxidation peak current value Ip0, certain density glyphosate is added in above-mentioned electrolytic cell, and in kind carry out differential pulse
Measurement, measures oxidation peak current value Ip1And calculate peak current difference △ Ip1；
2. the glyphosate standard solution of various concentration according to said method, is added, corresponding peak point current I can be obtainedpnThe peak and
Current differential △ IPn, peak current difference △ IpnGood linear relationship is presented with glyphosate concentration, can detect the linear of glyphosate
Range is 10-12~10-5Mol/L, linear equation are △ Ip(μ A)=8.0241+ 0,4301lgc(mol/L), c is concentration, single
Position is mol/L, peak current IpUnit is μ A, and linearly dependent coefficient r=0.9951 detects and is limited to 6.0 × 10-13mol/L；
3. calculating the concentration of unknown glyphosate using above-mentioned linear equation: in the PBS buffer solution containing 10mlpH=6.0
With 10-4mol/L NO2 -Electrolytic cell in, with PAMAM-C60- MWCNT-AuNPs/GCE is working electrode, and Ag/AgCl electrode is
Reference electrode, platinum electrode are to electrode；Experiment carries out on CHI760B electrochemical workstation, soft using its attached computer
The acquisition and processing of part progress experimental data；Differential pulse scanning is carried out first in 0.6-1.0V potential range, record shows difference
Pulse Voltammetry figure obtains peak point current Ip0, a certain amount of glyphosate solution to be measured is added, similarity condition is scanned, and obtains peak current
Value Ipn, peak current difference △ I is calculatedp, by △ IpIt brings above-mentioned equation into, the dense of solution glyphosate to be measured can be calculated
Degree.
Glyphosate residue problem is worldwide widely present, and causes chronic lasting harm, previous inspection to organism
The instrument for needing complicated pre-treatment step and Large expensive is surveyed, on-site test is inconvenient, and higher cost.The present invention prepares step
Rapid simple, cost is relatively low, high sensitivity, and stability is good reusable, small in size that on-site test may be implemented, can be with sensitive fast
The residue of glyphosate in various samples is detected fastly.
Claims (3)
1. a kind of method of Electrochemical Detection glyphosate, it is characterised in that utilize fullerene, multi-walled carbon nanotube, Jenner's grain of rice
Son, PAMAM synthetic composite material PAMAM-C60- MWCNT-AuNPs, and with its modified electrode, modified electrode is examined for selectivity
Survey glyphosate.
2. a kind of method of Electrochemical Detection glyphosate according to claim 1, it is characterised in that utilize fullerene, multi wall
Carbon nanotube, gold nanoparticle, PAMAM synthetic composite material PAMAM-C60- MWCNT-AuNPs, and it is used for modified electrode, tool
Body step are as follows:
It takes 120mg to be graphitized hydroxylated multi-walled carbon nanotubes, the 45mL concentrated sulfuric acid and 15mL concentrated nitric acid is added, it is 2 hours ultrasonic, later
Centrifugation is washed with water until pH=6, multi-walled carbon nanotube after must handling in magnetic agitation 12 hours at 90 DEG C；Inject 1.2mL ice
Cold NaBH4(0.1M), which is arrived, contains 0.25mM sodium citrate and 0.25mM HAuCl4Aqueous solution in, stir 6 hours；Processing
Multi-walled carbon nanotube (MWCNT) and gold nanoparticle (AuNPs) are mixed 6 hours by 1:10 afterwards；Take 1.0mg PAMAM in magnetic
Power is added with stirring in 1.0mL ultrapure water, and 4.0mL ethyl alcohol is then added and continues to stir to get evenly dispersed solution, then will
Above-mentioned mixed solution is added to the C of 1.0mL 1.0mg/mL60In toluene solution, it is continuously stirred at room temperature 36 hours, uses respectively
Ethyl alcohol, secondary water washed once to obtain PAMAM-C60；PAMAM-C60It is mixed 6 hours and obtains with MWCNT-AuNPs
PAMAM-C60-MWCNT-AuNPs。
3. a kind of method of Electrochemical Detection glyphosate described in -2 any claims according to claim 1, it is characterised in that
Electrochemical Detection glyphosate senses the foundation of system, specific steps are as follows:
(1) PAMAM-C for taking 15 μ L to make60For-MWCNT-AuNPs drop coating on glass-carbon electrode, naturally dry obtains modified electrode
PAMAM-C60-MWCNT-AuNPs/GCE；In the PBS buffer solution of the pH=6.0 containing 10mL and 10-4mol/L NO2 -Electrolytic cell
In, with PAMAM-C60- MWCNT-AuNPs/GCE is working electrode, and Ag/AgCl electrode is reference electrode, and platinum electrode is to electrode；
It is tested using CHI760B electrochemical workstation, the acquisition and processing of experimental data utilize its subsidiary computer software, into
The potential region of row differential pulse voltammetry scanning is set as 0.6-1.0V, records complete differential pulse voltammetry figure, measures oxidation
Peak point current Ip0, certain density glyphosate is added in above-mentioned electrolytic cell, and in kind carry out differential pulse measurement, surveys
Obtain oxidation peak current value Ip1And calculate peak current difference △ Ip1；
(2) according to said method, the glyphosate standard solution of various concentration is added, corresponding peak point current I can be obtainedpnAnd peak current
Difference △ IPn, peak current difference △ IpnGood linear relationship is presented with glyphosate concentration, can detect the range of linearity of glyphosate
It is 10-12~10-5Mol/L, linear equation are △ Ip(μ A)=8.0241+0.4301lgc (mol/L), c is concentration, and unit is
Mol/L, peak current IpUnit is μ A, linearly dependent coefficient r=0.9951, and detection is limited to 6.0 × 10-13mol/L；
(3) concentration of unknown glyphosate is calculated using above-mentioned linear equation: containing 10mLpH=6.0 PBS buffer solution and
10-4mol/L NO2 -Electrolytic cell in, with PAMAM-C60- MWCNT-AuNPs/GCE is working electrode, and Ag/AgCl electrode is ginseng
Than electrode, platinum electrode is to electrode；Experiment carries out on CHI760B electrochemical workstation, uses its attached computer software
Carry out the acquisition and processing of experimental data；Differential pulse scanning is carried out first in 0.6-1.0V potential range, record shows poor arteries and veins
Voltammogram is rushed, peak point current I is obtainedp0, a certain amount of glyphosate solution to be measured is added, similarity condition is scanned, and obtains peak point current
Ipn, peak current difference △ I is calculatedp, by △ IpIt brings above-mentioned equation into, the concentration of solution glyphosate to be measured can be calculated.
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| CN108333233B (en) * | 2018-02-02 | 2020-04-21 | 李维嘉 | Method for rapidly detecting fenvalerate pesticide residue in soil |
| CN110988072B (en) * | 2019-12-20 | 2021-12-24 | 肇庆学院 | Single-walled carbon nanohorn @ hydroxylated multi-walled carbon nanotube electrochemical sensor and application thereof in detection of nitenpyram |
| CN114324515B (en) * | 2021-12-01 | 2022-09-27 | 江南大学 | Electrochemical sensor for detecting glyphosate based on copper porphyrin metal organic framework modified carbon paper electrode |
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